Letter

www.acsami.org

Red-Emissive Carbon Dots for Fingerprints Detection by Spray

Method: Coffee Ring Effect and Unquenched Fluorescence in Drying
Process
Jie Chen, Ji-Shi Wei, Peng Zhang, Xiao-Qing Niu, Wei Zhao, Ze-Yang Zhu, Hui Ding,
and Huan-Ming Xiong*
Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai
200433, P. R. China
*
S Supporting Information

ABSTRACT: Brightly red fluorescent carbon dots are synthe-

sized hydrothermally and dissolved in diluted hydrochloric acid
solution. Such carbon dots exhibit excitation-independent
emission at about 620 nm with quantum yield over 10%,
which is visible in daylight. After the carbon dots solution is
sprayed to the fingerprints on various solid substrates and dried
in air, clear fingerprints can be seen under an ultraviolet lamp and
stay stable for 1 day. Detailed characterizations suggest that
during the drying process, the coffee-ring effect and the
electrostatic interactions between the carbon dots and the
fingerprint residues prevent the typical aggregation-induced
fluorescence quenching of carbon dots.
KEYWORDS: carbon dot, fluorescence, fingerprint, visualization, coffee ring effect

F ingerprints analyses have provided reliable evidence for

criminal investigations for more than a century.1,2 When a
finger touches a solid surface, eccrine sweat and oily sebum will
has not been performed successfully before. Third, only CD-
based hybrid powders have been reported for LFPs detection,21
but their fluorescence are too weak to be seen by naked eyes,
leave an imprint of the finger’s ridge patterns. Such an imprint and brushing nanoparticles powder will destroy the fingerprint
is named latent fingerprint (LFP) because it cannot be seen details and risk the health of the examiners.5 Finally, as for the
clearly by the naked eyes, and thus the goal of fingerprints CD dispersion mediums, water usually cannot adhere stably on
detection is to enhance the visualization of LFPs.3 To date, many glossy surfaces, whereas organic solvents often destroy
various methods have been developed on the basis of chemical LFPs. Therefore, it is still a challenge to light up LFPs by CDs
or physical interactions between the chosen reagents with the in a simple, portable, safe, clear, and compatible way.
fingerprint residues.4−7 These methods include powder dusting, In the present research, we synthesized red-emissive
fluorescent dye staining, cyanoacrylate/iodine fuming, and fluorescent CDs (R-CDs) hydrothermally and applied them
vacuum metal deposition.8 Among them, fluorescence staining to visualize LFPs by a simple spraying method. The background
is a general approach for LFPs detection with high sensitivity.5 fluorescence interference is minimized by the red-emission, and
Typical fluorescent materials, such as organic dyes,9 conjugated
the typical aggregation-induced fluorescence quenching of CDs
polymers,10 quantum dots,11 and rare earth complexes,12 have
was overcome and utilized ingeniously. After careful inves-
been reported for this application.
tigations on the enhanced LFPs, we found the R-CDs were
Fluorescent carbon dots (CDs) have attracted much
attention in the past decade because of their low cost, green extracted into the tiny water droplets which located at the edges
synthesis, stable luminescence, good biosafety, and environ- of fingerprints. Such an extraction process can be ascribed to
mental friendliness.13 Although CDs have been widely applied the coffee-ring effect during water vaporization and the
in bioimaging, drug delivery, fluorescence sensing, and electrostatic interactions between R-CDs and the fingerprint
analyses,14−19 there are few reports involving the LFPs residues. Our R-CDs are able to detect LFPs on many kinds of
detection by CDs.20−23 In fact, several obstacles are hindering solid surfaces, and thus they are promising for practical criminal
CDs application in LFP detection. First, most CDs are blue- investigations as a simple, fast, portable, and accurate tool.
green emitting, so that their fluorescence is interfered with by
self-fluorescence from substrates like paper and plastic. Second, Received: March 19, 2017
the fluorescence of CDs is always quenched by their Accepted: May 23, 2017
aggregation in the solid state,20 and thus the spraying method Published: May 24, 2017

© 2017 American Chemical Society 18429 DOI: 10.1021/acsami.7b03917

ACS Appl. Mater. Interfaces 2017, 9, 18429−18433
ACS Applied Materials & Interfaces Letter

Experimentally, the R-CDs was synthesized by hydrothermal

treatment of p-phenylenediamine and phosphorus acid. After
purification, 10 mg of R-CDs was dissolved in 10 mL of 0.1 M
hydrochloric acid aqueous solution. The solution was sealed
into a little spray bottle and sprayed onto the fingerprints. In
general, the developing time for R-CDs stained finger prints is
about half an hour at room temperature, while the optimal
record time for taking photos is about several hours. To clarify
structures and surface properties, which is crucial for
developing fingerprints, the as-prepared R-CDs were charac-
terized by various methods.

Figure 2. Photographs of R-CDs stained fingerprints on (A) glass

sheet, (B) aluminum foil, (C) leather, and (D) plastic pieces under UV
light, respectively. The ridge termination points (green) and the
bifurcation points (blue) are marked in A.

carboxyl carbons (COOH, 289.0 eV) are not observed in the

XPS of our sample. The O 1s band contains two peaks at 532.4
and at 536.2 eV for C−O and the absorbed oxygen or H2O,
respectively. The N 1s band can be deconvoluted into three
peaks at 399.2, 400.3, and 401.4 eV, representing amino N,
Figure 1. (A) TEM and (B) HRTEM images of R-CDs, and (C)
pyrrolic N, and graphite N, respectively, which indicates that
photoluminescent (PL) emission spectra of R-CDs under excitation the R-CDs have good dispersibility in acidic solution. The
light of different wavelengths (the inset legends). The inset photos are Fourier transform infrared (FTIR) spectra (Figure S2) show
the sample in room light (left) and under a UV lamp (right), O−H or N−H stretching vibrations at 3414 cm−1, CC or
respectively. CN vibrations at 1630 cm−1, and a broad band representing
oxygen-related groups like −OH and C−O at 1380−1290
cm−1.26 The sharp peak at 1500 cm−1 results from the -NH3+,
The TEM image (Figure 1A) shows that the R-CDs are indicating the R-CDs are apt to accept H+ ions in acidic
uniform and well dispersed with an average diameter of 2.4 nm, solutions to form positive nanoparticles. Such CDs have a zeta
whereas the HRTEM image of R-CDs (Figure 1B) presents the potential of 18.7 mV, distinguished from those conventional
lattice fringes with an average interplanar spacing of 0.21 nm, CDs with negatively charged surfaces. The positive surface
corresponding to the (101) lattice space of graphite.24 X-ray charge is very important for the fingerprints detection, because
photoelectron spectra (XPS) in the full range (Figure S1A) the residues of sweat and sebum are negatively charged.27
prove the existence of C 1s (285 eV), N 1s (400 eV), O 1s (532 The UV−visible absorption and fluorescence spectra of the
eV) and Cl 2p (198 eV).25 We can obtain from the XPS spectra R-CDs are shown in Figure S3. In the UV region, two
that the element contents are 69.79, 12.51, 9.91, and 7.80% for absorption maxima at 240 and 283 nm are corresponding to the
C, O, N, and Cl, respectively. In the high-resolution XPS π−π* transitions of CC and CN bonds of the aromatic
spectra (Figure S1B−D), the C 1s band can be deconvoluted rings, respectively. In the visible region, a broad absorption
into two peaks corresponding to sp2 carbons (CC, 284.6 eV) band within 360−600 nm can be assigned to the complicated
and sp3 carbons (C−O/C−N, 285.6 eV). Unlike most of the surface states of R-CDs. In Figure 1C, the emission peak at 622
reported CDs, carbonyl carbons (CO, 287.8 eV) and nm is independent of the excitation wavelengths, and its highest
18430 DOI: 10.1021/acsami.7b03917
ACS Appl. Mater. Interfaces 2017, 9, 18429−18433
ACS Applied Materials & Interfaces Letter

After one drop of R-CDs aqueous solution is dried on a clean

flat surface, a red circular stamp appears. This phenomenon is
the so-called “coffee-ring effect”, which discloses that as liquid
evaporation proceeds, the capillary flow outward from the
center of the liquid will bring the suspended particles to the
edge until almost all particles deposit to form a ring pattern.29
Further drying the substrate will cause the solid-state R-CDs
lose their red fluorescence due to the well-known aggregation
induced fluorescence quenching of CDs. However, if the
substrate is touched by fingers beforehand, the situation will
change dramatically. In Figure 2 A, although the R-CDs are
sprayed homogeneously on the glass sheet, only the ridges of
fingerprints show bright red patterns after drying, while the
regions in the fingerprint furrows and outside LFPs are not
fluorescent. The second-level details, such as the ridge
termination and bifurcation, can be also recognized. These
details form the basis of fingerprint identification in principle,
and they are critical in practical identification.7 The red
fluorescence of fingerprints are so strong that it can even
overcome the reflection light from the aluminum foil (Figure
2B) and the blue background fluorescence from leather (Figure
2C) and plastic (Figure 2D).
Figure 3. Confocal fluorescence images of the R-CDs stained
To study these interesting results deeply, we employed a
fingerprints on glass (A) in dark field after 30 min drying, and in laser scanning confocal microscope to observe the R-CD
(B) dark field and (C) bright field after 60 min drying, respectively. stained fingerprints on a glass sheet. After the glass sheet was
(D) Merged picture of B and C. sprayed and dried in air for 30 min, the dark-field image (Figure
3 A) clearly shows numerous tiny red droplets, whereas the
majority of fluorescent droplets are aggregated to the edges of
emission intensity is observed when the excitation wavelength fingerprints. This phenomenon can be explained by the coffee-
is set at 530 nm. The fluorescence excitation spectrum of R- ring effect, that as water vaporizes, R-CDs spayed into the other
CDs can be well overlapped with the absorption curve in the regions are forced to the edges of fingerprints where there is
visible region (Figure S3), indicating that the surface structures separation between the sebum-covering region and the no-
and states are responsible for the red emission. The sebum region. More interestingly, after another 30 min drying,
corresponding luminescent mechanism may be ascribed to most tiny red droplets disappeared, whereas the R-CDs at the
the surface molecular state fluorescence.28 The so-called surface edges of fingerprints remained luminescent (Figure 3B). The
molecular state fluorescence is regarded as one of the supposed bright-field image (Figure 3C) confirms some liquids are
origins of CDs fluorescence, which is related to the surface located at the edges of fingerprints, which can overlap perfectly
molecular groups on CDs and shows excitation-independent with the dark-field image (Figure 3 D). Therefore, the final
PL emission. Our R-CDs possess strong red fluorescence under results are ascribed to the fluorescence quenching of CDs when
UV light, and they can even emit red fluorescence in daylight at they changed from the liquid phase to the solid state. On one
lab. Their optimal quantum yield in aqueous solution is hand, because the lipid compounds in the fingerprint residues
measured to be 11.2% by an integrating sphere, which is are able to prevent water evaporation, those R-CDs solution
outstanding among the reported R-CDs. Therefore, both the sprayed into the fingerprints will be protected by lipids from
excitation-independent red fluorescence and the positively evaporation. On the other, the R-CDs solution sprayed into the
charged surface states of our R-CDs are beneficial to the gaps between fingerprints and the blank area outside finger-
following LFPs detection. prints will dry gradually, but during the drying process some R-

Scheme 1. Fluorescence Staining Process and Mechanism of R-CDs toward the Fingerprints on Solid Substrates

18431 DOI: 10.1021/acsami.7b03917

ACS Appl. Mater. Interfaces 2017, 9, 18429−18433
ACS Applied Materials & Interfaces Letter

CDs will be pushed to fingerprint edges due to the coffee-ring Alarm System and Latent Fingerprint Detection. ACS Nano 2016, 10,
effect, while the other R-CDs aggregate in the blank area and 10366−10372.
lose their fluorescence. It is known that the fingerprint residues (7) Xu, L. R.; Li, Y.; Wu, S. Z.; Liu, X. H.; Su, B. Imaging Latent
contain the negatively charged fatty acids, which might have Fingerprints by Electrochemiluminescence. Angew. Chem., Int. Ed.
2012, 51, 8068−8072.
electrostatic interactions27,30 with the positive R-CDs so as to
(8) Sodhi, G. S.; Kaur, J. Powder Method for Detecting Latent
coat the tiny water droplets by sebum. As a result, the sebum Fingerprints: A Review. Forensic Sci. Int. 2001, 120, 172−176.
coating prevents water evaporation and maintains the (9) Wang, K. R.; Yang, Z. B.; Li, X. L. High Excimer-State Emission
fluorescence of the R-CDs for a few days at room temperature. of Perylene Bisimides and Recognition of Latent Fingerprints. Chem. -
Scheme 1 illustrates the fluorescence staining process and the Eur. J. 2015, 21, 5680−5684.
unquenched fluorescence mechanism of our R-CDs, which are (10) Yoon, J. H.; Jin, Y. J.; Sakaguchi, T.; Kwak, G. Visualization of
based on the coffee-ring effect and the electrostatic interactions. Sweat Fingerprints on Various Surfaces Using a Conjugated
In summary, we synthesized a new kind of CDs with strong Polyelectrolyte. ACS Appl. Mater. Interfaces 2016, 8, 24025−24029.
red fluorescence and positive surface charges in water. They can (11) Ryu, S. J.; Jung, H. S.; Lee, J. K. Latent Fingerprint Detection
be sprayed onto various solid surfaces to show the LFPs clearly Using Semiconductor Quantum Dots as a Fluorescent Inorganic
under UV light. Although the aggregation-induced fluorescence Nanomaterial for Forensic Application. Bull. Korean Chem. Soc. 2015,
36, 2561−2564.
quenching is a universal problem for CDs, the LFPs stained by
(12) Wang, M.; Li, M.; Yu, A.; Wu, J.; Mao, C. Rare Earth
our R-CDs remained luminescence in air for a long time. Fluorescent Nanomaterials for Enhanced Development of Latent
Detailed characterizations disclosed the coffee-ring effect during Fingerprints. ACS Appl. Mater. Interfaces 2015, 7, 28110−28115.
water evaporation and the electrostatic interactions between R- (13) Lim, S. Y.; Shen, W.; Gao, Z. Q. Carbon Quantum Dots and
CDs and the fingerprint residues, which prevented the red Their Applications. Chem. Soc. Rev. 2015, 44, 362−381.
fluorescence at the fingerprint edges from quenching. Our (14) Jiang, K.; Sun, S.; Zhang, L.; Lu, Y.; Wu, A.; Cai, C.; Lin, H. Red,
present research provides an effective, rapid, portable, and user- Green, and Blue Luminescence by Carbon Dots: Full-Color Emission
friendly method for fingerprint detection. Tuning and Multicolor Cellular Imaging. Angew. Chem., Int. Ed. 2015,

■
*
ASSOCIATED CONTENT
S Supporting Information
54, 5360−5363.
(15) Cao, L.; Wang, X.; Meziani, M. J.; Lu, F. S.; Wang, H. F.; Luo, P.
J. G.; Lin, Y.; Harruff, B. A.; Veca, L. M.; Murray, D.; Xie, S. Y.; Sun, Y.
P. Carbon dots for multiphoton bioimaging. J. Am. Chem. Soc. 2007,
The Supporting Information is available free of charge on the 129, 11318−11319.
ACS Publications website at DOI: 10.1021/acsami.7b03917. (16) Zheng, M.; Liu, S.; Li, J.; Qu, D.; Zhao, H. F.; Guan, X. G.; Hu,
Details of the experiments and characterization results of X. L.; Xie, Z. G.; Jing, X. B.; Sun, Z. C. Integrating Oxaliplatin with
XPS, FTIR, DLS, UV−vis, Raman, PL spectra, and Highly Luminescent Carbon Dots: An Unprecedented Theranostic
CLSM images (PDF) Agent for Personalized Medicine. Adv. Mater. 2014, 26, 3554−3560.

■
(17) Li, G. L.; Fu, H. L.; Chen, X. J.; Gong, P. W.; Chen, G.; Xia, L.;
Wang, H.; You, J. M.; Wu, Y. N. Facile and Sensitive Fluorescence
AUTHOR INFORMATION Sensing of Alkaline Phosphatase Activity with Photoluminescent
Corresponding Author Carbon Dots Based on Inner Filter Effect. Anal. Chem. 2016, 88,
*E-mail: [email protected]. 2720−2726.
ORCID (18) Chen, H.; Xie, Y. J.; Kirillov, A. M.; Liu, L. L.; Yu, M. H.; Liu, W.
S.; Tang, Y. A Ratiometric Fluorescent Nanoprobe Based on Terbium
Ji-Shi Wei: 0000-0002-0605-040X Functionalized Carbon Dots for Highly Sensitive Detection of an
Huan-Ming Xiong: 0000-0002-3118-942X Anthrax Biomarker. Chem. Commun. 2015, 51, 5036−5039.
Notes (19) Baptista, F. R.; Belhout, S. A.; Giordani, S.; Quinn, S. J. Recent
The authors declare no competing financial interest. Developments in Carbon Nanomaterial Sensors. Chem. Soc. Rev. 2015,

■ ACKNOWLEDGMENTS
This work was financially supported by National Major Basic
44, 4433−4453.
(20) Xu, M.; He, G.; Li, Z.; He, F.; Gao, F.; Su, Y.; Zhang, L.; Yang,
Z.; Zhang, Y. A Green Heterogeneous Synthesis of N-doped Carbon
Dots and Their Photoluminescence Applications in Solid and Aqueous
Research Program of China (2013CB934101) and the States. Nanoscale 2014, 6, 10307−10315.
Shanghai Science and Technology Committee (21) Fernandes, D.; Krysmann, M. J.; Kelarakis, A. Carbon Dot Based
(16DZ2270100).

■
Nanopowders and Their Application for Fingerprint Recovery. Chem.
Commun. 2015, 51, 4902−4905.
REFERENCES (22) Wang, C. I.; Wu, W. C.; Periasamy, A. P.; Chang, H. T.
(1) Oden, S.; Von Hofsten, B. Detection of Fingerprints by the Electrochemical Synthesis of Photoluminescent Carbon Nanodots
Ninhydrin Reaction. Nature 1954, 173, 449−450. from Glycine for Highly Sensitive Detection of Hemoglobin. Green
(2) Jickells, S. M. Fingerprinting: Into the Future. Meas. Control Chem. 2014, 16, 2509−2514.
2008, 41, 243−247. (23) Dilag, J.; Kobus, H.; Yu, Y.; Gibson, C. T.; Ellis, A. V. Non-toxic
(3) Hazarika, P.; Russell, D. A. Advances in Fingerprint Analysis. Luminescent Carbon Dot/Poly(dimethylacrylamide) Nanocomposite
Angew. Chem., Int. Ed. 2012, 51, 3524−3531. Reagent for Latent Fingermark Detection Synthesized via Surface
(4) Leggett, R.; Lee-Smith, E. E.; Jickells, S. M.; Russell, D. A. Initiated Reversible Addition Fragmentation Chain Transfer Polymer-
″Intelligent″ Fingerprinting: Simultaneous Identification of Drug ization. Polym. Int. 2015, 64, 884−891.
Metabolites and Individuals by Using Antibody-functionalized Nano- (24) Liu, J.; Liu, Y.; Liu, N. Y.; Han, Y. Z.; Zhang, X.; Huang, H.;
particles. Angew. Chem., Int. Ed. 2007, 46, 4100−4103. Lifshitz, Y.; Lee, S. T.; Zhong, J.; Kang, Z. H. Metal-free Efficient
(5) Xu, L.; Zhang, C.; He, Y.; Su, B. Advances in the Development Photocatalyst for Stable Visible Water Splitting via a Two-electron
and Component Recognition of Latent Fingerprints. Sci. China: Chem. Pathway. Science 2015, 347, 970−974.
2015, 58, 1090−1096. (25) Ding, H.; Yu, S. B.; Wei, J. S.; Xiong, H. M. Full-Color Light-
(6) Jie, Y.; Zhu, H. R.; Cao, X.; Zhang, Y.; Wang, N.; Zhang, L. Q.; Emitting Carbon Dots with a Surface-State-Controlled Luminescence
Wang, Z. L. One-Piece Triboelectric Nanosensor for Self-Triggered Mechanism. ACS Nano 2016, 10, 484−491.

18432 DOI: 10.1021/acsami.7b03917

ACS Appl. Mater. Interfaces 2017, 9, 18429−18433
ACS Applied Materials & Interfaces Letter

(26) Wei, J. S.; Ding, H.; Zhang, P.; Song, Y. F.; Chen, J.; Wang, Y.
G.; Xiong, H. M. Carbon Dots/NiCo2O4 Nanocomposites with
Various Morphologies for High Performance Supercapacitors. Small
2016, 12, 5927−5934.
(27) Gao, F.; Han, J. X.; Zhang, J.; Li, Q.; Sun, X. F.; Zheng, J. C.;
Bao, L. R.; Li, X.; Liu, Z. L. The Synthesis of Newly Modified CdTe
Quantum Dots and Their Application for Improvement of Latent
Fingerprint Detection. Nanotechnology 2011, 22, 075705.
(28) Pan, L. L.; Sun, S.; Zhang, L.; Jiang, K.; Lin, H. W. Near-infrared
Emissive Carbon Dots for Two-photon Fluorescence Bioimaging.
Nanoscale 2016, 8, 17350−17356.
(29) Yunker, P. J.; Still, T.; Lohr, M. A.; Yodh, A. G. Suppression of
the Coffee-ring Effect by Shape-dependent Capillary Interactions.
Nature 2011, 476, 308−311.
(30) Wang, F.; Chen, J.; Zhou, H.; Li, W.; Zhang, Q.; Yu, C. Facile
Detection of Latent Fingerprints on Various Substrates Based on
Perylene Probe Excimer Emission. Anal. Methods 2014, 6, 654−657.

18433 DOI: 10.1021/acsami.7b03917

ACS Appl. Mater. Interfaces 2017, 9, 18429−18433